An Estimation of the Levels of Stabilized Criegee Intermediates in the UK Urban and Rural Atmosphere Using the Steady-State Approximation and the Potential Effects of These Intermediates on Tropospheric Oxidation Cycles

M Anwar H Khan; William C Morris; Matthew Galloway; Beth M A Shallcross; Carl J Percival; Dudley E Shallcross

doi:10.1002/kin.21101

An Estimation of the Levels of Stabilized Criegee Intermediates in the UK Urban and Rural Atmosphere Using the Steady-State Approximation and the Potential Effects of These Intermediates on Tropospheric Oxidation Cycles

Int J Chem Kinet. 2017 Aug;49(8):611-621. doi: 10.1002/kin.21101. Epub 2017 Jun 12.

Authors

M Anwar H Khan¹, William C Morris¹, Matthew Galloway¹, Beth M A Shallcross², Carl J Percival³, Dudley E Shallcross¹

Affiliations

¹ Atmospheric Chemistry Research Group School of Chemistry University of Bristol Bristol BS8 1TS UK.
² School of Pharmacy The University of Manchester Manchester, M13 9PL UK.
³ NASA Jet Propulsion Laboratory Pasadena CA 91109.

Abstract

Levels of the stabilized Criegee Intermediate (sCI), produced via the ozonolysis of unsaturated volatile organic compounds (VOCs), were estimated at two London urban sites (Marylebone Road and Eltham) and one rural site (Harwell) in the UK over the period of 1998-2012. The steady-state approximation was applied to data obtained from the NETCEN (National Environmental Technology Centre) database, and the levels of annual average sCI were estimated to be in the range of 30-3000 molecules cm^-3 for UK sites. A consistent diurnal cycle of sCI concentration is estimated for the UK sites with increasing levels during daylight hours, peaking just after midday. The seasonal pattern of sCI shows higher levels in spring with peaks around May due to the higher levels of O₃. The ozone weekend effect resulted in higher sCI in UK urban areas during weekend. The sCI data were modeled using the information provided by the Air Quality Improvement Research Program (AQIRP) and found that the modeled production was five- to six-fold higher than our estimated data, and therefore the estimated sCI concentrations in this study are thought to be lower estimates only. Compared with nighttime, 1.3- to 1.8-fold higher sCI exists under daytime conditions. Using the levels of sCI estimated at Marylebone Road, globally the oxidation rates of NO₂ + sCI (22.4 Gg/yr) and SO₂ + sCI (37.6 Gg/yr) in urban areas can increase their effect in the troposphere and potentially further alter the oxidizing capacity of the troposphere. Further investigations of modeled sCI show that CH₃CHOO (64%) and CH₂OO (13%) are dominant among all contributing sCI at the UK sites.